Formation of conjugated polymers for solid-state devices

ABSTRACT

Disclosed herein is a facile process for the formation of conjugated polymers inside or outside assembled solid-state devices. One process generally involves applying a voltage to a device comprising at least two electrodes, a combination of an electrolyte composition and a electroactive monomer disposed between the electrodes, and a potential source in electrical connection with the at least two electrodes; wherein the applying voltage polymerizes the electroactive monomer into a conjugated polymer. Also disclosed are electrochromic articles prepared from the process and solid-state devices comprising a composite of an electrolyte composition and a conjugated polymer.

CROSS REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional Application Ser.No. 61/317,457 filed Mar. 25, 2010, which is hereby incorporated byreference in its entirety.

TECHNICAL FIELD

The present invention is in the field of electrochromic devices, andmore specifically, in the field of electrochromic devices utilizing aconjugated polymer formed inside or outside an assembled solid-statedevice.

BACKGROUND

An electrochromic device is a self-contained, two-electrode (or more)electrolytic cell that includes an electrolyte and one or moreelectrochromic materials. Electrochromic materials can be organic orinorganic, and reversibly change visible color when oxidized or reducedin response to an applied electrical potential. Electrochromic devicesare therefore constructed so as to modulate incident electromagneticradiation via transmission, absorption, or reflection of the light uponthe application of an electric field across the electrodes. Theelectrodes and electrochromic materials used in the devices aredependent on the type of device, i.e., absorptive/transmissive orabsorptive/reflective.

Absorptive/transmissive electrochromic devices typically operate byreversibly switching the electrochromic materials between colored andbleached (colorless) states. Typical electrochromic materials used inthese devices include indium-doped tin oxide (ITO), fluorine-doped tinoxide (SnO₂:F), poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate)(PEDOT-PSS), and single-walled carbon nanotubes (SWNT). An exemplaryelectrochromic device of this type has been constructed using asubstrate layer of polyethylene terephthalate (PET), a transparent layerof ITO as the working electrode, and a third layer of PEDOT-PSS as thecounter electrode.

The absorptive/reflective-type electrochromic devices typically containa reflective metal as an electrode. The electrochromic material isdeposited onto this electrode and is faced outward to allow incidentlight to reflect off the electrochromic material/electrode surface. Thecounter electrode is behind the active electrode. Similar electrode andelectrochromic materials can be used in these reflective devices, inparticular ITO and PEDOT-PSS.

Traditionally built electrochromic devices utilizing an electrochromicpolymer have a discrete electrochromic polymer layer assembled with anelectrolyte on top. Devices are assembled between two electrodes usingthe electrolyte between them to achieve the necessary ion shuttling forthe redox-active electrochromic polymers. This electrolyte is oftencross-linked into a gel.

In traditional processes to prepare the foregoing electrochromic devicesusing an electrochromic polymer such as PEDOT, the electrochromicpolymer is formed into a discrete thin film prior to device assembly.Typical processes to prepare the thin film are via electrodeposition,spin or spray casting from solutions, etc. Drawbacks to usingelectrodeposition include the use of costly and wasteful electrolytebaths, the need for the frequent changing of organic salts and solventsin the baths, as well as the need for proper disposal of spent baths.Electrodeposition processes are also known to have poor yields.

Other processes besides electrodeposition involve complex syntheses togenerate soluble versions of an electrochromic polymer which can then becast and assembled into a device. The use of so-called precursorpolymers can be used in a casting process and then converted to theirelectrochromic counterpart. However, such a process still involved theinitial preparation of an electrochromic polymer film prior to deviceassembly.

There remains a need in the art for processes to prepare electrochromicdevices. There also remains a need for electrochromic devices havingimproved properties.

BRIEF SUMMARY

In one embodiment, a method of forming a solid-state device comprisesapplying voltage to a device comprising at least two electrodes, acombination of an electrolyte composition and an electroactive monomer,the combination disposed between the at least two electrodes, and apotential source in electrical connection with the at least twoelectrodes; wherein the applying voltage polymerizes the electroactivemonomer to form a composite comprising conjugated polymer andelectrolyte composition.

In one embodiment, a method of forming a solid-state device comprisesapplying voltage to a device comprising at least two electrodes, acombination of a crosslinked gel electrolyte composition and anelectroactive monomer, the combination disposed between the at least twoelectrodes, and a potential source in electrical connection with the atleast two electrodes; wherein the applying voltage polymerizes theelectroactive monomer to form a composite comprising conjugated polymerand crosslinked gel electrolyte composition.

In yet another embodiment, a solid-state device comprises at least twoelectrodes; and a composite disposed between the at least twoelectrodes, the composite comprising a conjugated polymer and anelectrolyte composition; wherein the composite is formed by in situpolymerization of an electroactive monomer in a combination comprisingthe electrolyte composition and an electroactive monomer.

In still another embodiment, a solid-state device comprises at least twoelectrodes; and a composite disposed between the at least twoelectrodes, the composite comprising a conjugated polymer and acrosslinked gel electrolyte composition; wherein the composite is formedby in situ polymerization of an electroactive monomer in a combinationcomprising the crosslinked gel electrolyte composition and anelectroactive monomer, wherein the conjugated polymer is not formed as adiscrete film.

BRIEF DESCRIPTION OF THE DRAWINGS

The components in the drawings are not necessarily to scale, emphasisinstead being placed upon clearly illustrating the principles of theembodiments described herein. Moreover, in the drawings, like referencenumerals designate corresponding parts throughout the several views.

FIG. 1 is a schematic of a procedure for the in situ polymerization of aelectroactive monomer into a conjugated, conducting, electrochromicpolymer inside an assembled solid-state device.

FIG. 2 illustrates the UV-Vis-NIR spectrum for a device containing insitu formed PEDOT: oxidized state (A) and neutral state (B) (Photopiccontrast: 40%).

FIG. 3 illustrates the spectroelectrochemistry for a poly(BTD-co-EDOT)device, Solid line=neutral state (0 V); dashed line=oxidized state (3V).

FIG. 4(A) illustrates an in situ PEDOT device with Ag wire as referenceelectrode.

FIG. 4(B) illustrates absorbance at 1500 nm during the conversionprocess and charges consumed for an in situ PEDOT device with Ag wire asreference electrode.

FIG. 4(C) illustrates the chronocoulometry of an in situ PEDOT devicewith Ag wire as reference electrode switching after conversion.

FIG. 5(A)-(D) illustrate images of inkjet patterned in situelectrochromic devices.

DETAILED DESCRIPTION

Disclosed herein is a facile, cost effective, and industrially scalablemethod for the formation of solid-state devices comprising a conjugatedpolymer by the in situ polymerization of an electroactive monomer. Asused herein, a conjugated polymer is synonymous to an electrochromicpolymer, an electroactive polymer, or a conducting polymer. Theconjugated polymer is formed inside the solid-state device by applying avoltage to the device to polymerize the electroactive monomer present ina mixture comprising a combination of an electrolyte composition andelectroactive monomer. The device can be fully assembled prior to theapplication of the voltage which effects the formation of the conjugatedpolymer via electrochemical polymerization. Such a process avoids manyof the usual processing steps required to make such solid-state devices(e.g., an electrochromic device (ECD). Such steps that are avoidedinclude formation of a discrete, thin film of conjugated polymer on asubstrate, formation of an electrolyte bath used for electrodeposition,disposal of the electrolyte bath, etc. There is also no need for specialprocessing steps for device assembly, special synthetic steps forconjugated polymer preparation, and there is a significant avoidance ofchemical waste in that electrolytic baths containing solvents andorganic salts are not used.

Also disclosed herein are solid-state devices prepared from the method.To prepare a device, only a mixture that comprises a combination of anelectroactive monomer and an electrolyte composition is needed. Unliketraditionally formed conjugated polymer films prepared viaelectrochemical deposition that are then used to form an assembleddevice, the conjugated polymer is not formed as a discrete thin-film,but rather a polymer composite with the electrolyte composition. Forexample, when a gel electrolyte is used, the conjugated polymer isformed as a composite with the gel electrolyte matrix. With thisprocess, it is possible to form a variety of complex blends.

Exemplary solid-state devices which can be prepared include ECDs,organic thin-film transistors (OTFTs), organic light-emitting diodes(OLEDs), solar cells, and organic photovoltaic cells (OPVs), the devicesdescribed further herein, below, and other solid-state devices.

A further advantage of the process is that it can be used with solid orliquid electroactive monomers by selecting the appropriate electrolytecomposition that would dissolve or disperse the electroactive monomer.Other advantages include the simplicity of color tuning via color mixingobtained by the copolymerization of various electroactive monomers.Still a further advantage is the formation of higher Photopic contrastwhen in situ polymerization is used, particularly when the electroactivemonomers are electropolymerized within the composite of crosslinkedelectrolyte matrix and electroactive monomer. Not wishing to be bound bytheory, it is hypothesized that the formation of a higher Photopiccontrast is due to less pi-pi stacking between the conjugated polymerchains, caused by the physical conformation of the polymer composite.Inter-chain interactions are therefore separated, and in the oxidized(conducting, bleached) state, this results in less inter-chain mobilityof the holes (absence of electrons) meaning there are fewer low-energyabsorptions that will contribute to visible absorption in the oxidizedstate and ultimately a higher Photopic contrast is observed.

When in situ polymerization is used, it was unexpected that an opticallyeven layer of conjugated polymer could be prepared in an assembled,sealed device as the presence of the crosslinked gel electrolyte acrossthe surface of the electrode would seem to be a barrier. However, thedevices prepared according to the instant process using a monomer withinthe gel electrolyte show an unprecedented evenness. The formation of theaforementioned composite in the matrix accounts for this evenness.

In one embodiment, a method to make a solid-state device comprisesproviding a device comprising at least two electrodes, a combination ofan electrolyte composition and an electroactive monomer disposed betweenthe electrodes, and a potential source in electrical connection with theat least two electrodes; and applying a voltage to the device topolymerize the electroactive monomer to form a composite of a conjugatedpolymer and electrolyte composition. Further within this embodiment, theproviding a device comprises mixing an electrolyte composition and anelectroactive monomer to form a combination of the electrolytecomposition and the electroactive monomer. The method further comprisesdisposing the combination of the electrolyte composition and theelectroactive monomer between the at least two electrodes.

When in situ polymerization is used, the application of a voltage causesdiffusive migration of the electroactive monomer present to the workingelectrode and the subsequent formation of the conjugated polymer in andaround the crosslinked matrix of the gel electrolyte to form acomposite. In another embodiment, a gel electrolyte precursor is usedand the voltage is applied to form the conjugated polymer prior to thecrosslinking of the gel electrolyte precursor to gel electrolyte. Inanother embodiment, the polymerization of the electroactive monomer andthe crosslinking of the gel electrolyte precursor are performed at thesame time.

The electrolyte compositions for use in the solid-state device includethose known for use in electrochromic devices. The electrolytecomposition may include metal salts, organic salts (e.g., ionicliquids), inorganic salts, and the like, and a combination thereof.

In one embodiment the electrolyte composition is a gel electrolyte. Thegel electrolyte layer can be formed by coating a gel electrolyteprecursor mixture comprising a gel electrolyte precursor. The gelelectrolyte precursor can be monomeric or polymeric. In particular, thegel precursor is a crosslinkable polymer. The crosslinkable polymer cancomprise polymerizable end groups, polymerizable side-chain groups, or acombination thereof attached to a polymer backbone. Exemplary polymerbackbones include polyamides, polyimides, polycarbonates, polyesters,polyethers, polymethacrylates, polyacrylates, polysilanes,polysiloxanes, polyvinylacetates, polymethacrylonitriles,polyacrylonitriles, polyvinylphenols, polyvinylalcohols,polyvinylidenehalides, and co-polymers and combinations thereof. Morespecifically, the gel precursor is a cross-linkable polyether. Exemplarypolyethers include poly(alkylene ethers) and poly(alkylene glycol)scomprising ethyleneoxy, propyleneoxy, and butyleneoxy repeating units.Hydroxyl end groups of poly(alkylene glycols) can be capped withpolymerizable vinyl groups including (meth)acrylate and styryl vinylgroups to form a crosslinkable polyether. In particular, thecrosslinkable polymer is selected from the group consisting ofpoly(ethylene glycol)diacrylate (PEG-DA), poly(propyleneglycol)diacrylate (PPG-DA), poly(butylene glycol)diacrylate (PBG-DA),poly(ethylene oxide) (PEO), poly(propylene oxide) (PPO), poly(butyleneoxide) (PBO), and combinations thereof. The crosslinkable polymer canalso be a copolymer or a block copolymer comprising ethyleneoxy,propylenoxy, or butyleneoxy repeating units. In one embodiment, the gelprecursor is PEO and is crosslinked thermally. In one embodiment, thegel precursor is PEO and is crosslinked using UV radiation. In aspecific embodiment, the gel precursor is crosslinkable polymercomprising a mixture of PEG-DA and PEO, wherein the PEO:PEG-DA weightratio is from 95:5 to 5:95, more particularly 90:10 to 10:90, and evenmore particularly 60:40 to 40:60 or 50:50.

The electrolyte composition can comprise an alkali metal ion of Li, Na,or K. Exemplary electrolytes, where M represents an alkali metal ion,include MClO₄, MPF₆, MBF₄, MAsF₆, MSbF₆, MCF₃SO₃, MCF₃CO₂, M₂C₂F₄(SO₃)₂,MN(CF₃SO₂)₂, MN(C₂F₅SO₂)₂, MC(CF₃SO₂)₃, MC_(n)F_(2n+1)SO₃ (2≦n≦3),MN(RfOSO₂)₂ (wherein Rf is a fluoroalkyl group), MOH, or combinations ofthe foregoing electrolytes. In particular, the electrolyte compositioncomprises a lithium salt. More particularly, the lithium salt is lithiumtrifluoromethanesulfonate. Other suitable salts includetetra-n-butylammonium tetrafluoroborate (TBABF₄); tetra-n-butylammoniumhexafluorophosphate (TBAPF₆); and combinations thereof. When a gelelectrolyte is used, the concentration of the electrolyte salt may beabout 0.01 to about 30% by weight of the gel electrolyte precursor,specifically about 5 to about 20% by weight, and yet more specificallyabout 10 to about 15% by weight of the gel electrolyte precursor.

The gel electrolyte precursor mixture can also comprise a solvent orplasticizer to enhance the ionic conductivity of the electrolyte. Thesemay be high boiling organic liquids such as carbonates, their blends orother materials like dimethylformamide (DMF). In particular the solventcan be a carbonate, for example alkylene and alkylyne carbonates such asdimethyl carbonate, ethylmethyl carbonate, methylpropyl carbonate,methylbutyl carbonate, methylpentyl carbonate, diethyl carbonate,ethylpropyl carbonate, ethylbutyl carbonate, dipropyl carbonate,propylene carbonate, ethylene carbonate, propylyne carbonate, andcombinations thereof. The amount of solvent and/or plasticizer added tothe gel electrolyte precursor mixture can range from about 0 to about50% by weight of the gel electrolyte precursor mixture, specificallyabout 10 to about 40% by weight, and more specifically about 20 to about30% by weight of the gel electrolyte precursor mixture.

The gel electrolyte precursor mixture can further comprise otheradditives such as photochemical sensitizers, free radical initiators,and diluent polymers, providing the desired properties of theelectrochromic device are not significantly adversely affected; forexample, the ionic conductivity of the gel electrolyte, the switchingspeed of the electrochromic response, color contrast of theelectrochromic response, adhesion of the gel electrolyte to thesubstrate, and flexibility of the electrodes.

In one embodiment, the gel electrolyte precursor mixture does notcomprise a plasticizer. In another embodiment, the gel electrolyte doescomprise a plasticizer.

The electrolyte composition may contain an ionic liquid. Ionic liquidsare organic salts with melting points under about 100° C. Other ionicliquids have melting points of less than room temperature (˜22° C.).Examples of ionic liquids that may be used in the electrolytecomposition include imidazolium, pyridinium, phosphonium ortetralkylammonium based compounds, for example,1-ethyl-3-methylimidazolium tosylate, 1-butyl-3-methylimidazolium octylsulfate; 1-butyl-3-methylimidazolium 2-(2-methoxyethoxy)ethyl sulfate;1-ethyl-3-methylimidazolium bis(pentafluoroethylsulfonyl)imide;1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide;1-ethyl-3-methylimidazolium bromide; 1-ethyl-3-methylimidazoliumhexafluorophosphate; 1-butyl-3-methylimidazolium bromide;1-butyl-3-methylimidazolium trifluoromethane sulfonate;1,2-dimethyl-3-propylimidazolium tris(trifluoromethylsulfonyl)methide;1,2-dimethyl-3-propylimidazolium bis(trifluoromethylsulfonyl)imide;3-methyl-1-propylpyridinium bis(trifluormethylsulfonyl)imide;1-butyl-3-methylpyridinium bis(trifluormethylsulfonyl)imide;1-butyl-4-methylpyridinium chloride; 1-butyl-4-methylpyridiniumhexafluorophosphate; 1-butyl-4-methylpyridinium tetrafluoroborate;1-n-butyl-3-methylimidazolium hexafluorophosphate (n-BMIM PF₆);1-butyl-3-methylimidazolium tetrafluoroborate (BMIM BF₄); phosphoniumdodecylbenzenesulfonate; phosphonium methanesulfonate; and mixtures ofthese.

The amount of ionic liquid that can be used in the gel electrolyteprecursor mixture can range from about 10% to about 80% by weight,specifically about 20% to about 70% by weight, more specifically about30% to about 60% by weight, and yet more specifically about 40% to about50% by weight of the gel electrolyte precursor mixture.

The gel electrolyte precursor can be converted to a gel via radicalcrosslinking initiated by thermal methods, or in particular by exposureto ultraviolet (UV) radiation. In an exemplary embodiment, thewavelength of UV irradiation is about 365 nm although other wavelengthscan be used.

The gel electrolyte precursor mixture may comprise a thermal initiatoror a photoinitiator. Exemplary photoinitiators include benzophenone,2,2-dimethoxy-2-phenylacetophenone (DMPAP), dimethoxyacetophenone,xanthone, and thioxanthone. In one embodiment the initiator may include2,2-dimethoxy-2-phenyl-acetophenone (DMPAP).

Crosslinking may also be thermally induced at about 40° C. to about 70°C., specifically about 50° C. using a thermal initiator. Exemplarythermal initiators include peroxide initiators such as benzyl peroxide(BPO), or azo bis isobutylnitrile (AIBN).

In one embodiment, the gel electrolyte precursor mixture comprises theelectrolyte salt (e.g. metal salts, organic salts (e.g., ionic liquids),inorganic salts, or a combination thereof) and the gel precursor in aweight ratio of 1 to 10, with a 0.002 to 1 to 10 ratio of initiator toelectrolyte to gel precursor, by weight.

Exemplary gel polymer electrolytes include those described in U.S. Pat.No. 7,586,663 and U.S. Pat. No. 7,626,748, both to Radmard et al.

The electroactive monomer is polymerized in situ in the assembled deviceby applying voltage (oxidative potential) across the device. Theelectroactive monomer irreversibly converts to the conjugated polymerand can be switched as normal, with a moderate reduction in opticalcontrast.

Examples of suitable electroactive monomers include those known in theart to exhibit electroactivity when polymerized, including but notlimited to thiophene, substituted thiophene, carbazole,3,4-ethylenedioxythiophene, thieno[3,4-b]thiophene, substitutedthieno[3,4-b]thiophene, dithieno[3,4-b:3′,4′-d]thiophene,thieno[3,4-b]furan, substituted thieno[3,4-b]furan, bithiophene,substituted bithiophene, pyrrole, substituted pyrrole, acetylene,phenylene, substituted phenylene, naphthalene, substituted naphthalene,biphenyl and terphenyl and their substituted versions, phenylenevinylene (e.g., p-phenylene vinylene), substituted phenylene vinylene,aniline, substituted aniline, indole, substituted indole, the monomersdisclosed herein as structures (I)-(XXXI), combinations thereof, and thelike.

The electroactive monomer can be selected from cathodically coloringmaterials, anodically coloring materials, or a combination thereof.

Cathodically coloring materials have a band gap (E_(g)) less than orequal to 2.0 eV in the neutral state. A cathodically coloring materialchanges color when oxidized (p-doped). The change in visible color canbe from colored in the neutral state to colorless in the oxidized state,or from one color in the neutral state to a different color in theoxidized state. Cathodically coloring materials include, but are notlimited to, polymers derived from a 3,4-alkylenedioxyheterocycle such asan alkylenedioxypyrrole, alkylenedioxythiophene or alkylenedioxyfuran.These further include polymers derived from3,4-alkylenedioxyheterocycles comprising a bridge-alkyl substituted3,4-alkylenedioxythiophene, such as3,4-(2,2-dimethylpropylene)dioxythiophene (ProDOT-(Me)₂),3,4-(2,2-dihexylpropylene)dioxythiophene (ProDOT-(hexyl)₂), or3,4-(2,2-bis(2-ethylhexyl)propylene)dioxythiophene(ProDOT-(ethylhexyl)₂). Herein, “colored” means the material absorbs oneor more radiation wavelengths in the visible region (400 nm to 700 nm)in sufficient quantity that the reflected or transmitted visible lightby the material is visually detectable to the human eye as a color (red,green, blue or a combination thereof).

An anodically coloring material has a band gap E_(g) greater than 3.0 eVin its neutral state. An anodically coloring material changes color whenreduced (n-doped). The material can be colored in the neutral state andcolorless in reduced state, or have one color in the neutral state and adifferent color in the reduced state. An anodically coloring materialcan also comprise polymers derived from a 3,4-alkylenedioxyheterocycleor derived from an alkylenedioxyheterocycle such asalkylenedioxypyrrole, alkylenedioxythiophene or alkylenedioxyfuran.Exemplary 3,4-alkylenedioxyheterocycle monomers to prepare anodicallycoloring polymers include an N-alkyl substituted3,4-alkylenedioxypyrrole, such as N-propyl-3,4-propylenedioxypyrrole(N-Pr ProDOP), N-Gly-3,4-propylenedioxypyrrole (N-Gly ProDOP), whereN-Gly designates a glycinamide adduct of pyrrole group, or N-propanesulfonated ProDOP (ProDOP-NPrS).

In one embodiment EDOT is used to prepare a cathodically coloringconjugated polymer and3,6-bis(2-(3,4-ethylenedioxy)thienyl)-N-methylcarbazole (BEDOT-NMCz) isused to prepare an anodically coloring conjugated polymer which iscomplementary to PEDOT when on the counter electrode.

Suitable electroactive monomers include 3,4-ethylenedioxythiophene,3,4-ethylenedithiathiophene, 3,4-ethylenedioxypyrrole,3,4-ethylenedithiapyrrole, 3,4-ethylenedioxyfuran,3,4-ethylenedithiafuran, and derivatives having the general structure(I):

wherein each occurrence of Q¹ is independently S, O, or Se; Q² is S, O,or N—R² wherein R² is hydrogen or C₁-C₆ alkyl; and each occurrence of R¹is independently hydrogen, C₁-C₁₂ alkyl, C₁-C₁₂ alkyl-OH, C₁-C₁₂haloalkyl, C₁-C₁₂ alkoxy, C₁-C₁₂ haloalkoxy, aryl, —C₁-C₆ alkyl-O—C₁-C₆alkyl, or —C₁-C₆ alkyl-O-aryl. In one embodiment, each occurrence of R¹is hydrogen. In one embodiment, each Q¹ is O and Q² is S. In anotherembodiment, each Q¹ is O, Q² is S, and one R¹ is C₁-C₁₂ alkyl, C₁-C₁₂alkyl-OH, C₁-C₁₂ haloalkyl, C₁-C₁₂ alkoxy, C₁-C₁₂ haloalkoxy, —C₁-C₆alkyl-O—C₁-C₆ alkyl, while the remaining R¹ are hydrogen. In anotherembodiment, each Q¹ is O, Q² is S, and one R¹ is C₁ alkyl-OH, while theremaining R¹ are hydrogen. A specific electroactive monomer is3,4-ethylenedioxythiophene or EDOT.

Another suitable electroactive monomer includes an unsubstituted and 2-or 6-substituted thieno[3,4-b]thiophene and thieno[3,4-b]furan havingthe general structures (II), (III), and (IV):

wherein Q¹ is S, O, or Se; and R¹ is hydrogen, C₁-C₁₂ alkyl, C₁-C₁₂haloalkyl including perfluoroalkyl, C₁-C₁₂ alkoxy, C₁-C₁₂ haloalkoxy,aryl, —C₁-C₆ alkyl-O—C₁-C₆ alkyl, or —C₁-C₆ alkyl-O-aryl. In oneembodiment, Q¹ is S and R¹ is hydrogen. In another embodiment, Q¹ is Oand R¹ is hydrogen. In yet another embodiment, Q¹ is Se and R¹ ishydrogen.

Another suitable electroactive monomer includes substituted3,4-propylenedioxythiophene (PropOT) monomers according to the generalstructure (V):

wherein each instance of R³, R⁴, R⁵, and R⁶ independently is hydrogen;optionally substituted C₁-C₂₀ alkyl, C₁-C₂₀ haloalkyl, aryl, C₁-C₂₀alkoxy, C₁-C₂₀ haloalkoxy, aryloxy, —C₁-C₁₀ alkyl-O—C₁-C₁₀ alkyl,—C₁-C₁₀ alkyl-O-aryl, —C₁-C₁₀ alkyl-aryl; or hydroxyl. The C₁-C₂₀ alkyl,C₁-C₂₀ haloalkyl, aryl, C₁-C₂₀ alkoxy, C₁-C₂₀ haloalkoxy, aryloxy,—C₁-C₁₀ alkyl-O—C₁-C₁₀ alkyl, —C₁-C₁₀ alkyl-O-aryl, or —C₁-C₁₀alkyl-aryl groups each may be optionally substituted with one or more ofC₁-C₂₀ alkyl; aryl; halogen; hydroxyl; —N—(R²)₂ wherein each R² isindependently hydrogen or C₁-C₆ alkyl; cyano; nitro; —COOH; —S(═O)C₀-C₁₀alkyl; or —S(═O)₂C₀-C₁₀ alkyl. In one embodiment, R⁵ and R⁶ are bothhydrogen. In another embodiment, R⁵ and R⁶ are both hydrogen, eachinstance of R³ independently is C₁-C₁₀ alkyl or benzyl, and eachinstance of R⁴ independently is hydrogen, C₁-C₁₀ alkyl, or benzyl. Inanother embodiment, R⁵ and R⁶ are both hydrogen, each instance of R³independently is C₁-C₅ alkyl or benzyl and each instance of R⁴independently is hydrogen, C₁-C₅ alkyl, or benzyl. In yet anotherembodiment, each instance of R³ and R⁴ are hydrogen, and one of R⁵ andR⁶ is hydroxyl while the other is hydrogen.

Other suitable electroactive monomers include pyrrole, furan, thiophene,and derivatives having the general structure (VI):

wherein Q² is S, O, or N—R² wherein R² is hydrogen or C₁-C₆ alkyl; andeach occurrence of R¹ is independently hydrogen, C₁-C₁₂ alkyl, C₁-C₁₂haloalkyl, C₁-C₁₂ alkoxy, C₁-C₁₂ haloalkoxy, aryl, —C₁-C₆ alkyl-O—C₁-C₆alkyl, or —C₁-C₆ alkyl-O-aryl. An exemplary substituted pyrrole includesn-methylpyrrole. Exemplary substituted thiophenes include3-methylthiophene and 3-hexylthiophene.

Additional electroactive monomers include isathianaphthene,pyridothiophene, pyrizinothiophene, and derivatives having the generalstructure (VII):

wherein Q² is S, O, or N—R² wherein R² is hydrogen or C₁-C₆ alkyl; eachoccurrence of Q³ is independently CH or N; and each occurrence of R¹ isindependently hydrogen, C₁-C₁₂ alkyl, C₁-C₁₂ haloalkyl, C₁-C₁₂ alkoxy,C₁-C₁₂ haloalkoxy, aryl, —C₁-C₆ alkyl-O—C₁-C₆ alkyl, or —C₁-C₆alkyl-O-aryl.

Still other electroactive monomers include oxazole, thiazole, andderivatives having the general structure (VIII):

wherein Q¹ is S or O.

Additional electroactive monomers include the class of compoundsaccording to structure (IX):

wherein Q² is S, O, or N—R² wherein R² is hydrogen or C₁-C₆ alkyl; andeach occurrence of Q¹ is independently S or O.

Additional electroactive monomers (or oligomers) include bithiophene,bifuran, bipyrrole, and derivatives having the following generalstructure (X):

wherein each occurrence of Q² is independently S, O, or N—R² wherein R²is hydrogen or C₁-C₆ alkyl; and each occurrence of R¹ is independentlyhydrogen, C₁-C₁₂ alkyl, C₁-C₁₂ haloalkyl, C₁-C₁₂ alkoxy, C₁-C₁₂haloalkoxy, aryl, —C₁-C₆ alkyl-O—C₁-C₆ alkyl, or —C₁-C₆ alkyl-O-aryl.

Electroactive monomers (or oligomers) include terthiophene, terfuran,terpyrrole, and derivatives having the following general structure (XI):

wherein each occurrence of Q² is independently S, O, or N—R² wherein R²is hydrogen or C₁-C₆ alkyl; and each occurrence of R¹ is independentlyhydrogen, C₁-C₁₂ alkyl, C₁-C₁₂ haloalkyl, C₁-C₁₂ alkoxy, C₁-C₁₂haloalkoxy, aryl, —C₁-C₆ alkyl-O—C₁-C₆ alkyl, or —C₁-C₆ alkyl-O-aryl.

Additional electroactive monomers include thienothiophene, thienofuran,thienopyrrole, furanylpyrrole, furanylfuran, pyrolylpyrrole, andderivatives having the following general structure (XII):

wherein each occurrence of Q² is independently S, O, or N—R² wherein R²is hydrogen or C₁-C₆ alkyl; and each occurrence of R¹ is independentlyhydrogen, C₁-C₁₂ alkyl, C₁-C₁₂ haloalkyl, C₁-C₁₂ alkoxy, C₁-C₁₂haloalkoxy, aryl, —C₁-C₆ alkyl-O—C₁-C₆ alkyl, or —C₁-C₆ alkyl-O-aryl.

Still other electroactive monomers include dithienothiophene,difuranylthiophene, dipyrrolylthiophene, dithienofuran, dipyrrolylfuran,dipyrrolylpyrrole, and derivatives having the following generalstructure (XIII):

wherein each occurrence of Q² is independently S, O, or N—R² wherein R²is hydrogen or C₁-C₆ alkyl; Q⁴ is C(R¹)₂, S, O, or N—R²; and eachoccurrence of R¹ is independently hydrogen, C₁-C₁₂ alkyl, C₁-C₁₂haloalkyl, C₁-C₁₂ alkoxy, C₁-C₁₂ haloalkoxy, aryl, —C₁-C₆ alkyl-O—C₁-C₆alkyl, or —C₁-C₆ alkyl-O-aryl.

Additional electroactive monomers include dithienylcyclopentenone,difuranylcyclopentenone, dipyrrolylcyclopentenone and derivatives havingthe following general structure (XIV):

wherein each occurrence of Q² is independently S, O, or N—R² wherein R²is hydrogen or C₁-C₆ alkyl; and E is O or C(R⁷)₂, wherein eachoccurrence of R⁷ is an electron withdrawing group.

Other suitable electroactive monomers (or oligomers) include thosehaving the following general structure (XV):

wherein each occurrence of Q¹ is independently S or O; each occurrenceof Q² is independently S, O, or N—R² wherein R² is hydrogen or C₁-C₆alkyl; each occurrence of R¹ is independently hydrogen, C₁-C₁₂ alkyl,C₁-C₁₂ haloalkyl, C₁-C₁₂ alkoxy, C₁-C₁₂ haloalkoxy, aryl, —C₁-C₆alkyl-O—C₁-C₆ alkyl, or —C₁-C₆ alkyl-O-aryl. In one embodiment, eachoccurrence of Q¹ is O; each occurrence of Q² is S; and each occurrenceof R¹ is hydrogen.

Additional electroactive monomers (or oligomers) includedithienovinylene, difuranylvinylene, and dipyrrolylvinylene according tothe structure (XVI):

wherein each occurrence of Q² is independently S, O, or N—R² wherein R²is hydrogen or C₁-C₆ alkyl; each occurrence of R¹ is independentlyhydrogen, C₁-C₁₂ alkyl, C₁-C₁₂ haloalkyl, C₁-C₁₂ alkoxy, C₁-C₁₂haloalkoxy, aryl, —C₁-C₆ alkyl-O—C₁-C₆ alkyl, or —C₁-C₆ alkyl-O-aryl;and each occurrence of R⁸ is hydrogen, C₁-C₆ alkyl, or cyano.

Other electroactive monomers (or oligomers) include1,2-trans(3,4-ethylenedioxythienyl)vinylene,1,2-trans(3,4-ethylenedioxyfuranyl)vinylene,1,2-trans(3,4-ethylenedioxypyrrolyl)vinylene, and derivatives accordingto the structure (XVII):

wherein each occurrence of Q⁵ is independently CH₂, S, or O; eachoccurrence of Q² is independently S, O, or N—R² wherein R² is hydrogenor C₁-C₆ alkyl; each occurrence of R¹ is independently hydrogen, C₁-C₁₂alkyl, C₁-C₁₂ haloalkyl, C₁-C₁₂ alkoxy, C₁-C₁₂ haloalkoxy, aryl, —C₁-C₆alkyl-O—C₁-C₆ alkyl, or —C₁-C₆ alkyl-O-aryl; and each occurrence of R⁸is hydrogen, C₁-C₆ alkyl, or cyano.

Additional electroactive monomers (or oligomers) include the classbis-thienylarylenes, bis-furanylarylenes, bis-pyrrolylarylenes andderivatives according to the structure (XVIII):

wherein each occurrence of Q² is independently S, O, or N—R² wherein R²is hydrogen or C₁-C₆ alkyl; each occurrence of R¹ is independentlyhydrogen, C₁-C₁₂ alkyl, C₁-C₁₂ haloalkyl, C₁-C₁₂ alkoxy, C₁-C₁₂haloalkoxy, aryl, —C₁-C₆ alkyl-O—C₁-C₆ alkyl, or —C₁-C₆ alkyl-O-aryl;and

represents an aryl. Exemplary aryl groups include furan, pyrrole,N-substituted pyrrole, phenyl, biphenyl, thiophene, fluorene,9-alkyl-9H-carbazole, and the like.

Other electroactive monomers (or olgiomers) include the class ofbis(3,4-ethylenedioxythienyl)arylenes, related compounds, andderivatives according to the structure (XIX):

wherein each occurrence of Q¹ is independently S or O; each occurrenceof Q² is independently S, O, or N—R² wherein R² is hydrogen or C₁-C₆alkyl; each occurrence of R¹ is independently hydrogen, C₁-C₁₂ alkyl,C₁-C₁₂ haloalkyl, C₁-C₁₂ alkoxy, C₁-C₁₂ haloalkoxy, aryl, —C₁-C₆alkyl-O—C₁-C₆ alkyl, or —C₁-C₆ alkyl-O-aryl; and

represents an aryl.

Other exemplary electroactive monomers (or oligomers) includebis(3,4-ethylenedioxythienyl)arylenes according to structure (XIX)includes the compound wherein all Q¹ are O, both Q² are S, all R¹ arehydrogen, and

is phenyl linked at the 1 and 4 positions. Another exemplary compound iswhere all Q¹ are O, both Q² are S, all R¹ are hydrogen, and

is thiophene linked at the 2 and 5 positions (bisEDOT-thiophene).

Additional electroactive monomers (or oligomers) include the class ofcompounds according to structure (XX):

wherein each occurrence of Q¹ is independently S or O; each occurrenceof Q² is independently S, O, or N—R² wherein R² is hydrogen or C₁-C₆alkyl; Q⁴ is C(R¹)₂, S, O, or N—R²; and each occurrence of R¹ isindependently hydrogen, C₁-C₁₂ alkyl, C₁-C₁₂ haloalkyl, C₁-C₁₂ alkoxy,C₁-C₁₂ haloalkoxy, aryl, —C₁-C₆ alkyl-O—C₁-C₆ alkyl, or —C₁-C₆alkyl-O-aryl. In one embodiment, each occurrence of Q¹ is O; eachoccurrence of Q² is S; each occurrence of R¹ is hydrogen; and R² ismethyl.

Still other electroactive monomers (or oligomers) include the class ofcompounds according to structure (XXI):

wherein each occurrence of Q² is independently S, O, or N—R² wherein R²is hydrogen or C₁-C₆ alkyl; Q⁴ is C(R¹)₂, S, O, or N—R²; and eachoccurrence of R¹ is independently hydrogen, C₁-C₁₂ alkyl, C₁-C₁₂haloalkyl, C₁-C₁₂ alkoxy, C₁-C₁₂ haloalkoxy, aryl, —C₁-C₆ alkyl-O—C₁-C₆alkyl, or —C₁-C₆ alkyl-O-aryl.

Additional electroactive monomers include the class of compoundsaccording to structure (XXII):

wherein each occurrence of Q² is independently S, O, or N—R² wherein R²is hydrogen or C₁-C₆ alkyl; each occurrence of Q⁴ is C(R¹)₂, S, O, orN—R²; and each occurrence of R¹ is independently hydrogen, C₁-C₁₂ alkyl,C₁-C₁₂ haloalkyl, C₁-C₁₂ alkoxy, C₁-C₁₂ haloalkoxy, aryl, —C₁-C₆alkyl-O—C₁-C₆ alkyl, or —C₁-C₆ alkyl-O-aryl.

Other exemplary monomers (or oligomers) include the class of compoundsaccording to structure (XXIII):

wherein each occurrence of Q² is independently S, O, or N—R² wherein R²is hydrogen or C₁-C₆ alkyl; and each occurrence of Q¹ is independently Sor O.

Exemplary electroactive monomers include the class of compoundsaccording to structure (XXIV):

wherein Q² is S, O, or N—R² wherein R² is hydrogen or C₁-C₆ alkyl; eachoccurrence of Q¹ is independently S or O; and each occurrence of R¹ isindependently hydrogen, C₁-C₁₂ alkyl, C₁-C₁₂ haloalkyl, C₁-C₁₂ alkoxy,C₁-C₁₂ haloalkoxy, aryl, —C₁-C₆ alkyl-O—C₁-C₆ alkyl, —C₁-C₆ alkyl-aryl,—C₁-C₆ alkyl-O-aryl, or —C₁-C₆ alkyl-O-aryl. In one embodiment, one R¹is methyl and the other R¹ is benzyl, —C₁-C₆ alkyl-O-phenyl, —C₁-C₆alkyl-O-biphenyl, or —C₁-C₆ alkyl-biphenyl.

Additional electroactive monomers (or oligomers) include the class ofcompounds according to structure (XXV):

wherein each occurrence of Q² is independently S, O, or N—R² wherein R²is hydrogen or C₁-C₆ alkyl; each occurrence of Q¹ is independently S orO; and each occurrence of R¹ is independently hydrogen, C₁-C₁₂ alkyl,C₁-C₁₂ haloalkyl, C₁-C₁₂ alkoxy, C₁-C₁₂ haloalkoxy, aryl, —C₁-C₆alkyl-O—C₁-C₆ alkyl, or —C₁-C₆ alkyl-O-aryl. In one embodiment, one R¹is methyl and the other R¹ is —C₁-C₆ alkyl-O-phenyl or —C₁-C₆alkyl-O-biphenyl per geminal carbon center.

Other electroactive monomers (or oligomers) include the class ofcompounds according to structure (XXVI):

wherein each occurrence of Q² is independently S, O, or N—R² wherein R²is hydrogen or C₁-C₆ alkyl; each occurrence of Q¹ is independently S orO; each occurrence of R¹ is independently hydrogen, C₁-C₁₂ alkyl, C₁-C₁₂haloalkyl, C₁-C₁₂ alkoxy, C₁-C₁₂ haloalkoxy, aryl, —C₁-C₆ alkyl-O—C₁-C₆alkyl, or —C₁-C₆ alkyl-O-aryl; and

represents an aryl. In one embodiment, one R¹ is methyl and the other R¹is —C₁-C₆ alkyl-O-phenyl or —C₁-C₆ alkyl-O-biphenyl per geminal carboncenter.

Exemplary electroactive monomers include the class of compoundsaccording to structure (XXVII):

wherein each occurrence of Q² is independently S, O, or N—R² wherein R²is hydrogen or C₁-C₆ alkyl; each occurrence of Q¹ is independently S orO; and each occurrence of R¹ is independently hydrogen, C₁-C₁₂ alkyl,C₁-C₁₂ haloalkyl, C₁-C₁₂ alkoxy, C₁-C₁₂ haloalkoxy, aryl, —C₁-C₆alkyl-O—C₁-C₆ alkyl, or —C₁-C₆ alkyl-O-aryl.

Additional electroactive monomers include the class of compoundsaccording to structure (XXVIII):

wherein each occurrence of Q² is independently S, O, or N—R² wherein R²is hydrogen or C₁-C₆ alkyl; each occurrence of Q¹ is independently S orO; and each occurrence of R¹ is independently hydrogen, C₁-C₁₂ alkyl,C₁-C₁₂ haloalkyl, C₁-C₁₂ alkoxy, C₁-C₁₂ haloalkoxy, aryl, —C₁-C₆alkyl-O—C₁-C₆ alkyl, or —C₁-C₆ alkyl-O-aryl.

Another electroactive monomer includes aniline or substituted anilineaccording to structure (XXIX):

wherein g is 0, 1, 2, or 3; and each occurrence of R⁹ is independentlyC₁-C₁₂ alkyl, C₁-C₁₂ haloalkyl, C₁-C₁₂ alkoxy, C₁-C₁₂ haloalkoxy, aryl,—C₁-C₆ alkyl-O—C₁-C₆ alkyl, —C₁-C₆ alkyl-O-aryl, or N—R² wherein R² ishydrogen or C₁-C₆ alkyl.

Exemplary monomers include EDOT, PropOT,1,4-bis[(3,4-ethylenedioxy)thien-2-yl)]-2,5-didodecyloxybenzene(BEDOT-B), benzothiadiazole (BTD), thieno[3,4-b]thiophene,thieno[3,4-b]furan, combinations thereof, and the like.

In one embodiment, a single type of electroactive monomer is employed toform a homopolymer. In another embodiment, a combination of two or moreelectroactive monomer types is used in a copolymerization process toform a conducting copolymer. As used herein “conducting polymer” isinclusive of conducting homopolymers and conducting copolymers unlessotherwise indicated. Furthermore, in one embodiment, the polymerizationmay be conducted with a mixture of an electroactive monomer and anon-electroactive monomer. Color tuning can be achieved by the choice ofmonomers for copolymerization.

In another embodiment, a conducting oligomer, a viologen, a conductingpolymer precursor, or a combination thereof, can be used in the placeof, or in addition to, the electroactive monomer. It is to be understoodthat all embodiments that describe the use of monomers, there is thecorresponding embodiment wherein the monomer component is replaced witha conducting oligomer, a viologen, a conducting polymer precursor, or acombination thereof.

As used herein, viologens include a 4,4′-dipyridinium salt according tostructures (XXX) and (XXXI):

wherein each occurrence of R¹⁰ is independently C₁-C₁₂ alkyl, C₁-C₁₂haloalkyl, aryl, —C₁-C₆ alkyl-O—C₁-C₆ alkyl, or —C₁-C₆ alkyl-O-aryl; and

is U₂, U₄, or U₆ alkenylene, an aryl or heteroaryl, specifically two,three, four, or more aryl or heteroaryl groups lined together. Exemplary

is phenylene, thiophene, and ethylene.

As used herein, a conducting polymer precursor includes a polymer oroligomer that can undergo further chain growth and/or crosslinking toproduce the conjugated polymer.

Exemplary conducting polymer precursors include those of structures(XXXII) and (XXXIII):

wherein n is an integer greater than 0; y is 0, 1, or 2; Q² isindependently S, O, or N—R² wherein R² is hydrogen or C₁-C₆ alkyl; R¹¹is a C₁-C₂₀ alkylene group; Z is a silylene group, for example—Si(R¹²)₂— or —Si(R¹²)₂—O—Si(R¹²)₂—) wherein each R¹² independently is aC₁-C₂₀ alkyl; and R¹³ is C₁-C₂₀ alkyl, C₁-C₂₀ alkoxy, C₁-C₂₀ thioalkyl,or C₁-C₂₀ aryl attached at the 3 and/or 4 position (shown) of thefive-membered ring. R¹² can be, for example, methyl, ethyl, propyl,isopropyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, or n-octyl. ExemplaryR¹³ include methyl, ethyl, propyl, isopropyl, n-butyl, n-pentyl,n-hexyl, n-heptyl, n-octyl, phenyl, n-butylthio, n-octylthio-,phenylthio-, and methoxyphenyl.

In one embodiment, n is an integer from 1 to 1000, y is 0, R¹¹ isethylene (—CH₂CH₂—), each Q² is sulfur, Z is —Si(R¹²)₂—, and R¹² isn-octyl. This 2,5-bis[(3,4-ethylenedioxy)thien-2-yl]-thiophene (BEDOT-T)silylene precursor polymer can be formed by the nickel-catalyzedcoupling of 3,4-ethylenedioxythiophene with dibromothiophene, to formBEDOT-T, followed by deprotonation of BEDOT-T using n-BuLi to form adianion of BEDOT-T, and reacting the dianion with dichlorodioctylsilaneto form the BEDOT-T silylene precursor polymer. The weight averagemolecular weight of the BEDOT-T silylene precursor polymer can be 1000to 100,000 g/mole, more specifically 1,000 to 10,000 g/mole.

In another specific embodiment, n is an integer from 1 to 1000, y is 0,R¹¹ is 2,2-dimethylpropylene (—CH₂C(CH₃)₂CH₂—), each Q² is sulfur, Z is—Si(R¹²)₂—O—Si(R¹²)₂—, and R¹² is methyl. This PropOT-Me₂ silyleneprecursor polymer can be prepared by transesterification of3,4-dimethoxythiophene with 2,2-dimethyl-1,3-propanediol usingpara-toluene sulfonic acid (PTSA) or dodecylbenzene sulfonic acid (DBSA)as catalysts in anhydrous toluene to form PropOT-Me₂, deprotonating thePropOT-Me₂ using 2 equivalents of n-BuLi to form the dilithium dianion,and reacting the dilithium dianion with dichlorotetramethylsiloxane toform the PropOT-Me₂ silylene precursor polymer. The weight averagemolecular weight of the PropOT-Me₂ silylene precursor polymer can be1000 to 100,000 g/mole, more specifically 1,000 to 5000 g/mole.

In addition to the heterocyclic ring systems shown in the precursors offormulas (XXXII) and (XXXIII), other aromatic heterocycle groups, e.g.,those of formulas (I)-(XXVIII), can also be synthesized with silylene offormula Z.

Other suitable conducting polymer precursors include polynorbornyleneconducting polymer precursor having an electroactive group (e.g. anelectroactive monomer or oligomer such as those described above) graftedonto the polymer backbone. Exemplary polynorbornylene conducting polymerprecursors include those of structure (XXXIV):

wherein L is a linking group containing 1-6 carbon atoms optionallyinterrupted by O, S, N(R¹⁴)₂, OC═O, C═OO, OC═OO, NR¹⁴C═O, C═ONR¹⁴,NR¹⁴C═ONR¹⁴, and the like, wherein R¹⁴ is H, C₁-C₁₂ alkyl, C₁-C₁₂haloalkyl, aryl, —C₁-C₆ alkyl-O—C₁-C₆ alkyl, or —C₁-C₆ alkyl-O-aryl; EGis an electroactive group; p¹ is 0 or 1; p² is 0 or 1 with the provisothat at least one of p¹ and p² is 1; and m is about 3 to about 3000.

The polynorbornylene can be prepared by polymerization of a norbornylenemonomer such as structure (XXXV):

wherein L, EG, p¹ and p² are as defined above. The polymerization toform the polynorbornylene can be accomplished via ring openingmetathesis polymerization (ROMP) using an appropriate catalyst (e.g.Grubb's alkylidene catalyst).

Exemplary polynorbornylenes include those of structures (XXXVI) and(XXXVII):

In another embodiment, the norbornylene monomer is used in combinationwith the electroactive monomer rather than the polynorbornyleneconducting polymer precursor.

Additional electrochromic precursors are described, for example, in U.S.Pat. No. 7,321,012 to Sotzing, U.S. Patent Publs. 2007/0089845 toSotzing et al., 2007/0008603 to Sotzing et al., and WO2007/008977 toSotzing, the relevant disclosures of which are each incorporated byreference herein.

As used herein, electroactive oligomers include any dimer, trimer, orcompound having multiple heterocycle units in length, wherein theheterocycle is an electroactive monomer. Exemplary oligomers have 2 to10 units, specifically 2 to 7 units, and more specifically 2 to 3 units.

Compounds are described using standard nomenclature. For example, anyposition not substituted by any indicated group is understood to haveits valency filled by a bond as indicated, or a hydrogen atom. A dash(“-”) that is not between two letters or symbols is used to indicate apoint of attachment for a substituent. For example, “—CHO” is attachedthrough carbon of the carbonyl group.

Unless otherwise indicated, the term “substituted” as used herein meansreplacement of one or more hydrogens with one or more substituents.Suitable substituents include, for example, hydroxyl, C₆-C₁₂ aryl,C₃-C₂₀ cycloalkyl, C₁-C₂₀ alkyl, halogen, C₁-C₂₀ alkoxy, C₁-C₂₀alkylthio, C₁-C₂₀ haloalkyl, C₆-C₁₂ haloaryl, pyridyl, cyano,thiocyanato, nitro, amino, C₁-C₁₂ alkylamino, C₁-C₁₂ aminoalkyl, acyl,sulfoxyl, sulfonyl, amido, or carbamoyl.

As used herein, “alkyl” includes straight chain, branched, and cyclicsaturated aliphatic hydrocarbon groups, having the specified number ofcarbon atoms, generally from 1 to about 20 carbon atoms, greater than 3for the cyclic. Alkyl groups described herein typically have from 1 toabout 20, specifically 3 to about 18, and more specifically about 6 toabout 12 carbons atoms. Examples of alkyl include, but are not limitedto, methyl, ethyl, n-propyl, isopropyl, n-butyl, 3-methylbutyl, t-butyl,n-pentyl, and sec-pentyl. As used herein, “cycloalkyl” indicates amonocyclic or multicyclic saturated or unsaturated hydrocarbon ringgroup, having the specified number of carbon atoms, usually from 3 toabout 10 ring carbon atoms. Monocyclic cycloalkyl groups typically havefrom 3 to about 8 carbon ring atoms or from 3 to about 7 carbon ringatoms. Multicyclic cycloalkyl groups may have 2 or 3 fused cycloalkylrings or contain bridged or caged cycloalkyl groups. Examples ofcycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, orcyclohexyl as well as bridged or caged saturated ring groups such asnorbornane or adamantane.

As used herein “haloalkyl” indicates both branched and straight-chainalkyl groups having the specified number of carbon atoms, substitutedwith 1 or more halogen atoms, generally up to the maximum allowablenumber of halogen atoms (“perhalogenated”). Examples of haloalkylinclude, but are not limited to, trifluoromethyl, difluoromethyl,2-fluoroethyl, and penta-fluoroethyl.

As used herein, “alkoxy” includes an alkyl group as defined above withthe indicated number of carbon atoms attached through an oxygen bridge(—O—). Examples of alkoxy include, but are not limited to, methoxy,ethoxy, n-propoxy, i-propoxy, n-butoxy, 2-butoxy, t-butoxy, n-pentoxy,2-pentoxy, 3-pentoxy, isopentoxy, neopentoxy, n-hexoxy, 2-hexoxy,3-hexoxy, and 3-methylpentoxy.

“Haloalkoxy” indicates a haloalkyl group as defined above attachedthrough an oxygen bridge.

As used herein, the term “aryl” indicates aromatic groups containingonly carbon in the aromatic ring or rings. Such aromatic groups may befurther substituted with carbon or non-carbon atoms or groups. Typicalaryl groups contain 1 or 2 separate, fused, or pendant rings and from 6to about 12 ring atoms, without heteroatoms as ring members. Whereindicated aryl groups may be substituted. Such substitution may includefusion to a 5 to 7-membered saturated cyclic group that optionallycontains 1 or 2 heteroatoms independently chosen from N, O, and S, toform, for example, a 3,4-methylenedioxy-phenyl group. Aryl groupsinclude, for example, phenyl, naphthyl, including 1-naphthyl and2-naphthyl, and bi-phenyl.

As used herein “heteroaryl” indicates aromatic groups containing carbonand one or more heteroatoms chosen from N, O, and S. Exemplaryheteroaryls include oxazole, pyridine, pyrazole, thiophene, furan,isoquinoline, and the like. The heteroaryl groups may be substitutedwith one or more substituents.

As used herein, “halo” or “halogen” refers to fluoro, chloro, bromo, oriodo.

As used herein, “arylene” includes any divalent aromatic hydrocarbon ortwo or more aromatic hydrocarbons linked by a bond, a heteroatom (e.g.,O, S, S(═O), S(═O)₂, etc.), a carbonyl group, an optionally substitutedcarbon chain, a carbon chain interrupted by a heteroatom, and the like.

The electrolyte/electroactive monomer mixture may optionally include anadditional additive. The additive may be chosen so that it does not,unless desired, interfere with oxidative polymerization, interfere withcolor/contrast/switching, interfere with electrodes or other componentsin a degradative way. Exemplary additional additives may also be used inthe combination of electrolyte and electroactive monomer, and includeconductive fillers such as particulate copper, silver, nickel, aluminum,carbon black, graphene, carbon nanotubes, buckminister fullerene, andthe like; non-conductive fillers such as talc, mica, wollastonite,silica, clay, dyes, pigments (zeolites), and the like.

The solid-state devices may further include a variety of substratematerials (flexible or rigid) used to house the electrolyte/monomercombination. Exemplary substrate materials include glass, plastic,silicon, a mineral, a semiconducting material, a ceramic, a metal, andthe like, as well as a combination thereof. The substrate may beinherently conductive. Flexible substrate layers can be made fromplastic. Exemplary plastics include polyethylene terephthalate (PET),poly(arylene ether), polyamide, polyether amide, etc. The substrate mayinclude mirrored or reflective substrate material. A further advantageof the process is that the substrates do not require cleaning ascompared to ITO substrates which need to be vigorously cleaned prior toimmersion in an electrolyte bath otherwise any defect will causeunevenness of the film deposited.

Exemplary electrode materials for use in the electrochromic devices caninclude inorganic materials such as glass-indium doped tin oxide(glass-ITO), doped silicon, metals such as gold, platinum, aluminum, andthe like, metal alloys such as stainless steel (“SS”), SS 316, SS316L,nickel and/or cobalt alloys such as Hastelloy-B®(Ni62/Mo28/Fe5/Cr/Mn/Si), Hastelloy-C®, and the like; and organicmaterials such as a conjugated polymer such aspoly(3,4-ethylenedioxythiophene)-polystyrene sulfonate (PEDOT-PSS),conjugated polymers prepared from an electroactive monomer describedherein, carbon black, carbon nanotubes, graphene, and the like.

In one embodiment, all of the electrodes are polyethylene terephthalate(PET)/indium-doped tin oxide (ITO) substrates.

The solid-state device can generally be fabricated by encasing a layerof the combination of electrolyte composition and electroactive monomerbetween at least two electrodes, wherein the electrodes are inelectrical communication with the layer of the combination. In anexemplary generalized assembled solid-state device as shown in FIG. 1, alayer of a combination of electrolyte composition (exemplified here witha gel electrolyte precursor) and electroactive monomer (10) is disposedbetween a first electrode (20) and a second electrode (30) and further(10) is in electrical communication with (20) and (30). Further,substrate layers (40) and (50) encase (10), (20), and (30). Uponapplication of a voltage, the solid-state device of FIG. 1 includes alayer of a matrix containing electrolyte composition and conjugatedpolymer (5) disposed between a first electrode (20) and a portion ofelectrolyte composition (here a gel electrolyte formed by crosslinkingthe gel electrolyte precursor either before or after the application ofvoltage) (15); the first electrode (20) and second electrode (30) areain electrical communication with (15) and (5). Further, substrate layers(40) and (50) encase (5), (15), (20), and (30).

The combination of electrolyte composition and electroactive monomer canbe formed into a layer in the device by mixing the components to form adispersion or solution, and applying the mixture to a substrate viaconventional processes including ink jet printing, screen printing, rollto roll printing processes, reel to reel processing, spin coating,meniscus and dip coating, spray coating, brush coating, doctor bladeapplication, curtain casting, drop casting, and the like.

In one embodiment, a device is assembled comprising a combination of agel electrolyte precursor and an electroactive monomer disposed betweena first electrode and a second electrode.

In another embodiment, a device is assembled by disposing a combinationof a gel electrolyte precursor and a electroactive monomer on a firstelectrode, crosslinking the gel electrolyte precursor to form a layer ofcrosslinked gel electrolyte and electroactive monomer, then adding asecond layer of gel electrolyte precursor, optionally in combinationwith a electroactive monomer, on top of the layer of crosslinked gelelectrolyte and electroactive monomer, and assembling a second electrodeon the second layer to form a sealed, assembled device. Within thisembodiment, the electroactive monomers can be polymerized before orafter the crosslinking of the gel electrolyte precursor in the secondlayer. Such a device may form a dual-conjugated polymer device.Alternatively, monomers with different oxidation potentials may beexploited such that one material polymerizes on one electrode and thesecond is polymerized on the other electrode, each in situ.

The polymerization of the electroactive monomers (and optionalconducting oligomer, viologen, conducting polymer precursor, or acombination thereof) can be effected by cyclic voltammetry (trianglewave voltammetry), chronocoulometry/constant voltage,galvanostatic/constant current, or square-wave voltammetry (pulsed). Inseveral embodiments, a reference electrode is fabricated inside thedevice. The potential (voltage) is applied to one electrode of thedevice for a sufficient time to substantially deplete the monomer fromthe combination of electrolyte composition and electroactive monomer.The formation of the conjugated polymer occurs on one electrode side,via diffusion through the electrolyte composition. In one embodiment,the conjugated polymer is not a discrete, thin film layer, as can beformed using electrodeposition methods, but rather is a blend orcomposite within the electrolyte composition.

In several embodiments, the device comprises an internal referenceelectrode system to result in a three-electrode cell. In one embodiment,the internal reference electrode is a silver wire pseudo-referenceelectrode embedded within the device to control voltage and preventelectrode damage (e.g., ITO degradation due to over-oxidation).

In another embodiment, a sealing means (e.g. a gasket) is providedbetween two substrates or electrodes to form an electrochormic devicewherein an internal reference electrode is provided between the sealingmeans. The sealing means seals the device.

In one embodiment, by controlling the voltage, it may be possible toachieve layered color mixing of various monomers, to form dual-polymerdevices with different polymer composites being formed on alternateelectrodes, and to form complex gradient blends and copolymers. Varyingthe voltage, time of application, and/or method of polymerization, onemay achieve these architectures.

In yet another embodiment, a method comprises polymerizing a firstelectroactive monomer on a first electrode using a first potential andthen polymerizing a second electroactive monomer at a second electrodeat a second potential different than the first potential. Such a processmay create a dual-conjugated polymer device. Monomers with differentoxidation potentials may be exploited such that one material polymerizeson one electrode at one applied voltage and the second is polymerized onthe other electrode at another applied voltage, each in situ.

The devices can be sealed to prevent water, air, or other contaminantmaterials from entering the device, as well as to prevent loss ofelectrolyte composition/electroactive monomer or electrolytecomposition/conjugated polymer. Sealing can be accomplished using anadhesive such as a polyurethane based UV curable resin or other suitableadhesive used in the formation of electrochromic devices.

The devices can be patterned using a variety of techniques includingusing a blocking (aka “insulating”) layer of material (e.g. blockingmaterial applied by ink jet printing, spray-cast, etc.), drop-castpatterning, directed polymerization by the selective application ofvoltage, direct patterning, lithography, patterned electrode surfaces,and other related methods to result in the formation of complexelectrochromic devices. High-resolution images can be created using thepatterning. The entire region of the device can be patterned oralternatively, only a portion of the device. In one embodiment, thepattern generated may be in the form of a straight line, a curved line,a dot, a plane, or any other desirable geometrical shape. The patternmay be one dimensional, two dimensional or three dimensional if desiredand may be formed upon the surface of the combination of electrolytecomposition and conjugated polymer mixture as an embossed structure orembedded within (below) the surface of the combination.

The devices can be patterned using a blocking layer of material, such asa material that is insoluble in the electrolyte composition. Exemplaryblocking materials include polystyrene, etc. The blocking material canbe applied to the working electrode using spray-casting, drop-casting,ink jet, screen printing, roll to roll printing processes, reel to reelprocessing, spin coating, meniscus and dip coating, brush coating,doctor blade application, curtain casting, and the like. This layer nowblocks the electrical field produced within the device upon applicationof voltage, which results in no polymer forming in these areas. Thedevice, when in situ polymerized, will then be patterned around theblocking layer. When the device is switched, the blocking layer willremain constant as the electrochromic changes color around it. Theblocking layer may be loaded with a dye, such that in one state, theelectrochromic is the same color as the blocking layer but in anotherstate it is not, thus allowing for the patternedimage/lettering/numbering/etc to be reversibly “revealed” and“concealed” upon switching.

In the patterning process using selective application of voltage, anelectrochemical atomic force microscope (AFM) tip can be used as anexternal counter electrode to supply the voltage. In an alternativeembodiment, injection polymerization can be accomplished using a needleto supply both a voltage and the combination of an electroactive monomerand electrolyte composition.

In one embodiment, a nanolithographic pattern may be generated byutilizing electrochemical atomic force microscopy (AFM) to selectivelypolymerize the electroactive monomer. In this method, an AFM tip (coatedwith a conductor such as gold, platinum/iridium, carbon, optionallymodified with carbon nanotubes) is used as a counter electrode. The AFMtip is either brought into contact with the combination of electrolytecomposition and electroactive monomer or brought into the proximity ofthe combination of electrolyte composition and electroactive monomerwithout touching the combination, and a suitable voltage is appliedbetween the electrochemical AFM tip and the substrate, which promotespolymerization of the electroactive monomer contacted by (or brought inclose proximity to) the AFM tip.

In one embodiment, the device can be prepared with individuallyaddressable electrode systems, thus allowing for pixilation of a device.Such devices are useful for simple display applications.

The electrochromic devices are capable of displaying a still or animatedcolor image composed of a combination of red, green, and blue visiblelight. Displaying occurs typically by reflection or transmission ofvisible light rather than by emission when the electrochromic materialis subjected to an electrical potential.

In one embodiment, the device is a reflective-type device (e.g.,[Mirrored] aluminum or steel background/PET-ITO counter).

Typically, when each electrode comprises the same electrochromicmaterial, the electrodes display different colors simultaneously, due tothe electrochromic material undergoing oxidation at the cathode andreduction at the anode, a so-called “dual electrochromic” design.

The process disclosed herein can be used to prepare solid-state devicessuch as electrochromic devices, organic thin-film transistors, organiclight-emitting diodes, organic photovoltaic cells, and the like.Specific articles prepared from the devices include color-changingsunglasses, high-contrast sunglasses or goggles, windows devised forheat-modulation in skyscrapers/buildings or fashion-tinting,auto-dimming mirrors in automobiles and trucks, displays, or a varietyof other color-changing devices.

In one embodiment, the solid-state device comprises a single compositelayer of the conjugated polymer and electrolyte composition.

In another embodiment, the solid-state device comprises a dual-typeconfiguration wherein there is a second composite layer of conjugatedpolymer on the counter electrode. The second layer can be a composite ofa second conjugated polymer and second electrolyte composition. The useof two conjugated polymer layers allows for mixed colored states orenhanced contrast by using conjugated polymers with complementaryoptical characteristics. Within this embodiment, an electroactivemonomer which produces an anodically coloring polymer and anelectroactive monomer which produces a cathodically coloring polymer canbe used in the dual-type configuration. Exemplary dual-typeconfigurations are disclosed in U.S. Patent Publ. 2007/0008603 toSotzing et al. The following illustrative examples are provided tofurther describe the invention and are not intended to limit the scopeof the claimed invention.

EXAMPLES Example 1 In Situ Polymerization of EDOT in an AssembledSolid-State Device

A device was assembled using a glass/indium-doped tin oxide (ITO)substrate, a polyethylene terephthalate (PET)/ITO substrate, and anelectrolyte composition containing 1 gram lithiumtrifluoromethanesulfonate (LITRIF) salt, 5 grams of polyethylene glycoldiacrylate (PEG-DA; Mn=700) as the gel electrolyte precursor, 5 grams ofpropylene carbonate (PC) plasticizer, and 17.5 milligrams of2,2;-dimethoxyphenylacetophenone (DMPAP) UV-activated cross-linkingagent. To the electrolyte composition was mixed 250 milligrams of3,4-ethylenedioxythiophene (EDOT) as the electroactive monomer. PEG-DAis crosslinked using UV light 365 nm, 5.8 mW/cm² for about 15 minutes.

The device has been shown to switch optically at the same rate asdevices prepared with PEDOT films prepared by electrodeposition. Overthe course of 50 cycles, no perceived losses had occurred. The CIE Lu′v′color coordinates for the device containing in situ polymerized EDOTwere u′=0.19, v′=0.42 for the neutral state and u′=0.21, v′=0.48 for theoxidized state, different from other PEDOT films in that the oxidizedstate is much more transparent (closer to the white point on the CIEdiagram). Traditionally prepared films of PEDOT show a light-blueoxidized state.

Spectroelectrochemistry of the device yielded a Photopic contrast of40%, similar to those achieved for traditionally prepared PEDOT devices.It should be noted that the film thickness of the device in this Examplehas not been optimized, thus the Photopic contrast of an optimized filmthickness is expected to be higher. FIG. 2 shows the UV-Vis-NIR spectrumfor the device in its oxidized (A) and neutral states (B). There is aless-notable tail from the IR into the Visible region with this system,showing a much less blue oxidized state than traditional PEDOT filmsprepared via electrodeposition.

Example 2 In Situ Polymerization of EDOT in an Assembled Solid-StateDevice using an Ionic Liquid

A solid-state device similar to Example 1 was prepared using ionicliquid 1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF₆) in theelectrolyte composition with no plasticizer component.

Example 3 Exploration of the In Situ Polymerization of EDOT in anAssembled Solid-State Device before and after Crosslinking of the GelElectrolyte Precursor

Two solid-state devices similar to Example 1 were prepared using noplasticizer. In the first device, the gel electrolyte precursor iscrosslinked prior to the in situ polymerization of EDOT. In the seconddevice, a voltage is applied to polymerize EDOT prior to thecrosslinking of the gel electrolyte precursor. The second deviceexhibited a better switching speed (2-5 seconds) and a lower conversiontime (30 seconds), while the first device took up to 5 minutes to make afilm of PEDOT and exhibits over 25 seconds to switch. It has been shownthat the conjugated polymer can be prepared prior to or postcrosslinking of the gel electrolyte precursor allowing for more flexibledevice assembly processes.

Example 4 In situ Copolymerization of EDOT (Liquid) and BTD (Solid) inan Assembled Solid-State Device

A solid-state device similar to Example 1 was prepared by co-mixing asolid electroactive monomer benzothiadiazole (BTD), and a liquidelectroactive monomer EDOT into with the electrolyte composition. Thetwo electroactive monomers are then co-polymerized in situ. FIG. 3illustrates the spectroelectrochemistry for the BTD-EDOT device, showingthe suitability of copolymerization processes, as well as the use ofsolid and liquid electroactive monomers (BTD is a solid and EDOT is aliquid at room temperature). The solid line=neutral state (0 V) and thedashed line=oxidized state (3 V).

Example 5 In Situ Copolymerization of an Electroactive Monomer in anAssembled Reflective-Type Device

A reflective-type device was prepared with a steel substrate, a PET/ITOsubstrate (3″×3″ or 7.62 centimeter×7.62 centimeter) and a mixture of anelectrolyte composition and an electroactive monomer. The resultingdevice after polymerization of the electroactive monomer exhibited noiris effect.

Example 6 Use of a Reference Electrode in the In Situ Polymerization ofEDOT in an Assembled Solid-State Device

To investigate the potential actually applied on the working electrode,a device was assembled with a silver wire (reference electrode)incorporated inside the device (FIG. 4(A)). The electrolyte compositionwas prepared by combining 5 g of propylene carbonate, 5 g ofpoly(ethylene glycol)diacrylate (Mn=700), 1 g oftrifluoromethanesulfonate, 17.5 mg of DMPAP together and sonicating for15 min. EDOT was added to the electrolyte to make a 2.5 wt % solutionthat was drop-cast onto an ITO substrate. A second ITO substrate was puton top of the first with a rubber gasket glued between the twosubstrates. A silver (Ag) wire was placed between the rubber gasket andpartially immersed inside the electrolyte composition. The assembleddevice was then UV crosslinked at 365 nm. The Ag reference electrode wascalibrated to 0.225V vs. normal hydrogen electrode (NHE).

The crosslinked device was then applied a potential of 3V for 30 s andswitched between the voltage of 0-3V after polymerization.Electrochemistry was carried out using CHI 400 and 660 A potentiostats.Optical characterizations were carried out with a Varian Cary 5000UV-Vis-NIR spectrophotometer. The monomer was polymerized inside theassembled device under a +3V potential from the potentiostat withreference electrode shorted with the counter electrode. A +1.1V biaswith respect to Ag was found. The device was then switched betweenoxidized and neutral states between +3V and OV from the potentiostat.The OV was used to avoid polymerization on the counter electrode. Theabsorption at 1500 nm was monitored to indicate the degree of conversionas it is characteristic for the PEDOT. The kinetic spectrum and chargeconsumed are shown in FIG. 4(B); the increase in absorbance taperedwithin 30 s, meaning that majority of the polymer was formed during thisperiod, which matches the coulombic data. FIG. 4(C) illustrates thechronocoulometry of the device switching after conversion.

Devices with 0.2 wt % and 1 wt % EDOT loading were also assembled. Notethe 0.2 wt % EDOT is approximately the monomer concentration (0.1M) in atraditional electrodeposition bath. Each concentration used showedsimilar trends. Although conversion time increased with higher monomerloading, switching time remained constant as it is a diffusion process.All conversions resulted in continuous, blue-colored devices; higherEDOT loading led to darker blues. Different methods, such as cyclicvoltammetry, square wave, and bulk electrolysis were also used toconvert the monomer in situ and led to similar devices.

Example 7 Exploration of Electrolyte Plasticizer Content on the In SituPolymerization of EDOT in an Assembled Solid-State Device

Devices with different loading of propylene carbonate (PC) plasticizerwere fabricated to investigate the effect of plasticizer concentrationon diffusion. Electrolyte compositions with 0, 10%, 25% and 50% of PCwere used. Ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate(BMIMPF₆) was employed to replace the plasticizer and salt in theelectrolyte. Table 1 shows the time needed for conversion in situ andswitching speed of the devices as a function of different PC weightpercentages in the electrolyte composition and monomer loadings.

TABLE 1 Varying Electrolyte Composition PC wt % 0 10 25 50 ConversionTime, s 52.88 34.55 24.00 12.91 Switching Time, s 0.045 0.045 0.0450.045 Varying wt % EDOT 0.1 0.2 1.0 2.5 Conversion Time, s 11.26 11.6512.73 12.91 Switching Time, s 0.045 0.045 0.045 0.045

As shown in Table 1, the conversion time increased with lowerplasticizer concentration while switching speed remained the same. Bothconversion time and switching time were significantly longer as comparedto the normal gel electrolyte due to the high viscosity of the ionicliquid and slower diffusion rate.

Example 8 Determination of Conversion Yield

To assess the actual conversion yield inside the in situ device, theconverted device was disassembled and the polymer-containing electrolytewas soxhleted and the concentration of the EDOT was measured by UV-vis.Multiple headspace extraction GC-MS (MHE GC-MS), a technique that canexhaustively extract residual monomers from solid matrix, was alsoemployed as a parallel approach. Both methods showed undetectable changeof the monomer amount between the control group (Os conversion) and thesample group (30 s conversion). According to the most commonly acceptedDiaz's mechanism of the polymerization of conducting polymers, the ratiobetween the number of electrons and the monomers reacted is 2 to 1.Therefore, with the total charge consumed during the polymerization,assuming no side reactions and overoxidation, the amount of monomersthat were involved in the polymerization can be calculated. Assuming thedensity of PEDOT to be 1 g/cm³, for a device with initial EDOT loadingof ca. 18 mg, active area of 3.5 cm×4 cm, the conversion yield wascalculated to be ca. 0.5%, and the film thickness was estimated to be 65nm. Based on previous studies, there is a relation between the photopiccontrast and PEDOT film thickness. Based on these studies, the in situdevice possesses the photopic contrast of a ca. 75 nm thick film, whichconfirmed an early observation of the in situ device having highercontrast compared to its ex situ counterparts. It is worth noting thatalthough the yield value appears to be low, it is still comparable, ifnot better, to the traditional method. A 20 mL 10 mM EDOT solution bathwould have a 0.49% conversion yield to obtain a 100 nm thick, 3.4 cm×4cm film, as well as a large amount of solvent and salt that have to bediscarded after one use. Furthermore, the monomer left in the in situdevice does not affect the stability of the device compared to their exsitu counterparts after the initial break-in period.

Example 9 Patterned Devices, Inkjet Printing

A polystyrene University of Connecticut logo pattern was inkjet printedby a Dimatix DMP 2800 materials printer using polystyrene ink. Thepolystyrene ink was prepared by dissolving polystyrene pellets intoluene to form a 2 wt % solution. The pattern was jetted onto ITOsubstrates. Devices were assembled and converted as described beforeusing the inkjet patterned ITO substrates containing the polystyteneblocking layer. FIG. 5 shows images of positive (top) and negative(bottom) logo patterned in situ PEDOT device (top, (A) and (B)) andpoly(2,2-dimethyl-3,4-propylenedioxythiophene) (PPropOT-Me₂ (bottom, (C)and (D)) in neutral A), C) and oxidized B), D) states, respectively.

The patterned devices can be formed without the need for rigorouscleaning of substrates as is required using electrodeposition.Additionally, blockage of the substrate makes complex patterningpossible and facile. The high resolution of the inkjet technique allowsfor the fabrication of complex patterns and preserves all the details ofthe image. Different monomers can be used in the in situ process, thusmaking the process exceedingly versatile. Different thiophenes andpyrroles were tested with this approach, which resulted in devices ofpurple, red, blue, yellow, green, and brown colors. Monomers testedinclude 2,2-dimethyl-3,4-propylenedioxythiophene (PropOT-Me2);bis(3,4-ethylenedioxythienyl)thiophene (BEDOT-T);1,3-diisopropyl-3,4-propylenedioxythiophene; pyrrole; and N-methylpyrrole in different colored states.

The use of the terms “a” and “an” and “the” and similar referents in thecontext of describing the invention (especially in the context of thefollowing claims) are to be construed to cover both the singular and theplural, unless otherwise indicated herein or clearly contradicted bycontext. The terms “comprising”, “having”, “including”, and “containing”are to be construed as open-ended terms (i.e., meaning “including, butnot limited to”) unless otherwise noted. “Or” means and/or. Recitationof ranges of values herein are merely intended to serve as a shorthandmethod of referring individually to each separate value falling withinthe range, unless otherwise indicated herein, and each separate value isincorporated into the specification as if it were individually recitedherein. All ranges disclosed herein are inclusive and combinable. Themodifier “about” used in connection with a quantity is inclusive of thestated value and has the meaning dictated by the context (e.g., includesthe degree of error associated with measurement of the particularquantity).

The essential characteristics of the present invention are describedcompletely in the foregoing disclosure. One skilled in the art canunderstand the invention and make various modifications withoutdeparting from the basic spirit of the invention, and without deviatingfrom the scope and equivalents of the claims, which follow. Moreover,any combination of the above-described elements in all possiblevariations thereof is encompassed by the invention unless otherwiseindicated herein or otherwise clearly contradicted by context.

What is claimed is:
 1. A method of forming a solid-state device,comprising: applying voltage to a device comprising at least twoelectrodes, a combination of a crosslinked gel electrolyte compositionand an electroactive monomer, the combination disposed between the atleast two electrodes, and a potential source in electrical connectionwith the at least two electrodes; wherein the applying voltagepolymerizes the electroactive monomer to form a composite comprisingconjugated polymer and crosslinked gel electrolyte composition.
 2. Themethod of claim 1, wherein the crosslinked gel electrolyte compositioncomprises a lithium, sodium, or potassium salt, or an ionic liquid. 3.The method of claim 1, wherein the crosslinked gel electrolyte is formedby crosslinking a gel electrolyte precursor in the presence of theelectroactive monomer to form a layer of crosslinked gel electrolytecomprising the electroactive monomer.
 4. The method of claim 1, whereina layer of a second electrolyte composition is disposed between anelectrode and the combination of the crosslinked gel electrolytecomposition and electroactive monomer, wherein the layer of secondelectrolyte composition optionally further comprises a secondelectroactive monomer.
 5. The method of claim 4, wherein the applyingvoltage polymerizes the electroactive monomer, and the method furthercomprises applying a second voltage to polymerize the secondelectroactive monomer.
 6. The method of claim 1, wherein the devicefurther comprises a reference electrode.
 7. The method of claim 1,wherein the electroactive monomer is thiophene, substituted thiophene,carbazole, 3,4-ethylenedioxythiophene, thieno[3,4-b]thiophene,substituted thieno[3,4-b]thiophene, dithieno[3,4-b:3′,4′-d]thiophene,thieno[3,4-b]furan, substituted thieno[3,4-b]furan, bithiophene,substituted bithiophene, pyrrole, substituted pyrrole, acetylene,phenylene, substituted phenylene, naphthalene, substituted naphthalene,biphenyl and terphenyl and their substituted versions, phenylenevinylene (e.g., p-phenylene vinylene), substituted phenylene vinylene,aniline, substituted aniline, indole, substituted indole, or acombination thereof.
 8. The method of claim 1, wherein the electroactive monomer is

wherein each occurrence of Q¹ is independently S, O, or Se; Q² is S, O,or N—R²; each occurrence of Q³ is independently CH or N; Q⁴ is C(R¹)₂,S, O, or N—R²; each occurrence of Q⁵ is independently CH₂, S, or O; eachoccurrence of R¹ is independently hydrogen, C₁-C₁₂ alkyl, C₁-C₁₂alkyl-OH, C₁-C₁₂ haloalkyl, C₁-C₁₂ alkoxy, C₁-C₁₂ haloalkoxy, aryl,—C₁-C₆ alkyl-O—C₁-C₆ alkyl, or —C₁-C₆ alkyl-O-aryl; R² is hydrogen orC₁-C₆ alkyl; each occurrence of R³, R⁴, R⁵, and R⁶ independently ishydrogen; optionally substituted C₁-C₂₀ alkyl, C₁-C₂₀ haloalkyl, aryl,C₁-C₂₀ alkoxy, C₁-C₂₀ haloalkoxy, aryloxy, —C₁-C₁₀ alkyl-O—C₁-C₁₀ alkyl,—C₁-C₁₀ alkyl-O-aryl, —C₁-C₁₀ alkyl-aryl; or hydroxyl; each occurrenceof R⁷ is an electron withdrawing group; each occurrence of R⁸ isindependently hydrogen, C₁-C₆ alkyl, or cyano; each occurrence of R⁹ isindependently C₁-C₁₂ alkyl, C₁-C₁₂ haloalkyl, C₁-C₁₂ alkoxy, C₁-C₁₂haloalkoxy, aryl, —C₁-C₆ alkyl-O—C₁-C₆ alkyl, —C₁-C₆ alkyl-O-aryl, orN—R²; each occurrence of R¹⁰ is independently C₁-C₁₂ alkyl, C₁-C₁₂haloalkyl, aryl, —C₁-C₆ alkyl-O—C₁-C₆ alkyl, or —C₁-C₆ alkyl-O-aryl; Eis O or C(R⁷)₂;

represents an aryl;

is C₂, C₄, or C₆ alkelylene, an aryl or heteroaryl; and g is 0, 1, 2, or3.
 9. The method of claim 1, wherein the combination of crosslinked gelelectrolyte composition and electro active monomer further comprises aconducting oligomer, a conducting precursor polymer, a viologen, or acombination thereof.
 10. The method of claim 1, further comprisingpatterning the device using a blocking material; direct patterning;lithography; individually addressable electrodes; or directedpolymerization by the selective application of voltage.
 11. The methodof claim 1, wherein an electrochemical atomic force microscope (AFM) tipis used as an external working electrode to supply the voltage for theapplying.